Functionalized polymers containing polyamine succinimide for antifouling in hydrocarbon refining processes

ABSTRACT

A multipurpose chemical additives (MPC) is disclosed to mitigate fouling in hydrocarbon refinery processes, such as in a heat exchanger. A method for reducing fouling of a hydrocarbon is also disclosed that includes (i) providing a crude hydrocarbon for a refining process; and (ii) adding an additive to the crude hydrocarbon.

TECHNICAL FIELD

The disclosed subject matter relates to additives to reduce fouling ofcrude hydrocarbon refinery components, and methods and systems using thesame.

BACKGROUND

Crude Pre-Heat Train exchangers are used to heat the crude oil as partof the distillation process. The crude is run on one side oftube-and-shell exchangers and heated by the hot streams run on theopposite side. More typically, crude oil is run through the tube side ofthe exchangers, however, some refineries run crude through the shellside with the hot stream on the tube side. The crude oil is run througha series of exchangers leading to the desalter and then to theatmospheric furnace. Whole crude oil fouling within exchangers is costlyto the petroleum industry due to reduced throughput, energy losses dueto needed increased furnace firing and higher cleaning and maintenancecosts. In some cases, unplanned unit shut-downs occur due to foulingwhich adds to the high costs of fouling. To mitigate fouling addition ofadditives known as anti-foulant additives to crude oil before heatexchanger is a common practice.

Multi-purpose additives can reduce cost in the refining operation.Petroleum refineries incur additional energy costs, perhaps billions peryear, due to fouling and the resulting attendant inefficiencies causedby the fouling. More particularly, thermal processing of crude oils,blends and fractions in heat transfer equipment, such as heatexchangers, is hampered by the deposition of insoluble asphaltenes andother contaminants (i.e., particulates, salts, etc.) that may be foundin crude oils. Further, the asphaltenes and other organics are known tothermally degrade to coke when exposed to high heater tube surfacetemperatures.

Fouling in heat exchangers receiving petroleum-type process streams canresult from a number of mechanisms including chemical reactions,corrosion, deposit of existing insoluble impurities in the stream, anddeposit of materials rendered insoluble by the temperature difference(ΔT) between the process stream and the heat exchanger wall. Forexample, naturally-occurring asphaltenes can precipitate from the crudeoil process stream, thermally degrade to form a coke and adhere to thehot surfaces. Further, the high ΔT found in heat transfer operationsresult in high surface or skin temperatures when the process stream isintroduced to the heater tube surfaces, which contributes to theprecipitation of insoluble particulates. Another common cause of foulingis attributable to the presence of salts, particulates and impurities(e.g., inorganic contaminants) found in the crude oil stream. Forexample, iron oxide/sulfide, calcium carbonate, silica, sodium chlorideand calcium chloride have all been found to attach directly to thesurface of a fouled heater rod and throughout the coke deposit. Thesesolids promote and/or enable additional fouling of crude oils.

The buildup of insoluble deposits in heat transfer equipment creates anunwanted insulating effect and reduces the heat transfer efficiency.Fouling also reduces the cross-sectional area of process equipment,which decreases flow rates and desired pressure differentials to provideless than optimal operation. To overcome these disadvantages, heattransfer equipment is ordinarily taken offline and cleaned mechanicallyor chemically cleaned, resulting in lost production time.

There is a need to reduce precipitation/adherence of particulates andasphaltenes from the heated surface to prevent fouling, particularlybefore the asphaltenes are thermally degraded or coked. Such reductionwill improve the performance of the heat transfer equipment, decrease oreliminate scheduled outages for fouling mitigation efforts, and reduceenergy costs associated with the processing activity.

Antifoulant additives have been described in a number of commonly-ownedapplications, including U.S. Patent Application Publication Nos.20110147275 and 20100170829, the disclosure of each of which isincorporated herein by reference in its entirety. However, there remainsa need for alternative antifoulant additives capable of reducingprecipitation and/or adherence of particulates and asphaltenes.

SUMMARY

The disclosed subject matter provide multipurpose chemical additives(MPC) to mitigate fouling in hydrocarbon refinery processes, such as ina heat exchanger. In accordance with one aspect of the disclosed subjectmatter, a method for reducing fouling a hydrocarbon is provided. Themethod includes (i) providing a crude hydrocarbon for a refiningprocess; and (ii) adding an additive to the crude hydrocarbon, theadditive being represented by one of Formula A and Formula B below:

wherein in each of Formula A and Formula B above:

m is an integer between 0 and 10 inclusive;

R₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenyl group;

R₂ is a C₁-C₄ branched or straight chained alkylene group;

R₃ is a C₁-C₄ branched or straight chained alkylene group;

R₃₁ is hydrogen or —R₈-R₉, wherein R₈ is C₁-C₄ branched or straightchained alkylene group, and R₉ is

wherein R₉₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup; or R₈ and R₉ together are a C₁-C₄ branched or straight chainedalkyl group optionally substituted with one or more amine groups; andfurther wherein the —N(R₃₁)—R₃— repeat unit is optionally interrupted inone or more places by a nitrogen-containing heterocyclic cycloalkylgroup; and

R₄ and R₅ are each independently selected from (a) hydrogen; (b) a bondconnected to R₃₁ in the last distal —N(R₃₁)—R₃— repeat unit; or (c)—R₆-R₇, wherein R₆ is C₁-C₄ branched or straight chained alkylene group,and R₇ is

wherein R₇₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup;

wherein in Formula B, n is an integer between 0 and 10 inclusive, andthe groups R₂′, R₃′, R₃₁′, R₄′ and R₅′ are each defined the same as R₂,R₃, R₃₁ and R₄, and R₅, respectively;

wherein in Formula B, z is 1 or 2, and y is an integer between 1 and 5inclusive.

According to another aspect of the disclosed subject matter, a compoundof Formula A as noted above is provided.

According to another aspect of the disclosed subject matter, a methodfor preparing a compound for reducing fouling of a crude hydrocarbon ina hydrocarbon refining process is provided. The method includes:

(a) reacting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, with maleic anhydride to obtain a polymer represented by FormulaI below:

wherein R₂₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup;

(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)-R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)-R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

According to a further aspect of the disclosed subject matter, acompound prepared by the above method is provided.

According to another aspect of the disclosed subject matter, a methodfor reducing fouling in a hydrocarbon refinery process is provided. Themethod includes: providing a crude hydrocarbon for a refining process;and adding an additive to the crude hydrocarbon, the additiverepresented by Formula A.

According to another aspect of the disclosed subject matter, a compoundof Formula B as noted above is provided.

In a further aspect, a method for preparing a compound of Formula B forreducing fouling of a crude hydrocarbon in a hydrocarbon refiningprocess is provided. The method includes:

(a) reacting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, with maleic anhydride to obtain a polymer represented by FormulaII below:

wherein R₂₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, z is 1 or 2, and y is an integer between 1 and 5 inclusive;

(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)-R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)-R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

In a further aspect, a compound prepared by the above method isprovided.

In yet a further aspect, a method for reducing fouling in a hydrocarbonrefinery process is provided. The method includes: providing a crudehydrocarbon for a refining process; and adding an additive to the crudehydrocarbon, the additive represented by formula B.

In addition, the disclosed subject matter provides compositionscomprising such additives, and systems for refining hydrocarbonscontaining such additives and compositions.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosed subject matter will now be described in conjunction withthe accompanying drawings in which:

FIG. 1 is a representation of an oil refinery crude pre-heat train,annotated to show non-limiting injection points for the additives of thedisclosed subject matter.

FIG. 2 is a schematic of the Alcor Hot Liquid Process Simulator (HLPS)employed in Example 3 of this application.

FIG. 3 is a graph demonstrating the effects of fouling of a controlcrude oil blend sample and a dehydrated crude oil blend sample treatedwith approximately 50 wppm of an additive according to the disclosedsubject matter, as measured by the Alcor HLPS apparatus depicted in FIG.2.

FIG. 4 is a graph demonstrating the effects of fouling of a controlcrude oil blend sample and a dehydrated crude oil blend sample treatedwith approximately 50 wppm of an additive according to the disclosedsubject matter, as measured by the Alcor HLPS apparatus depicted in FIG.2.

FIG. 5 is a graph demonstrating the effects of fouling of a controlcrude oil blend sample and a crude oil blend sample treated with 25 wppmof an additive according to the disclosed subject matter, as measured bythe Alcor HLPS apparatus depicted in FIG. 2.

FIG. 6 is a graph demonstrating the effects of fouling of a controlcrude oil blend sample and a crude oil blend sample treated with 50 wppmof an additive according to the disclosed subject matter, as measured bythe Alcor HLPS apparatus depicted in FIG. 2.

FIG. 7 is a graph demonstrating the effects of fouling of a controlcrude oil blend sample and a crude oil blend sample treated with 50 wppmof an additive according to the disclosed subject matter, as measured bythe Alcor HLPS apparatus depicted in FIG. 2.

FIG. 8 is a graph demonstrating the effects of fouling of a controlcrude oil blend sample and a crude oil blend sample treated with 50 wppmof an additive according to the disclosed subject matter, as measured bythe Alcor HLPS apparatus depicted in FIG. 2.

FIG. 9 is a graph demonstrating the effects of fouling of a controlcrude oil blend sample and a crude oil blend sample treated with 50 wppmand 25 wppm of an additive according to the disclosed subject matter, asmeasured by the Alcor HLPS apparatus depicted in FIG. 2.

DETAILED DESCRIPTION Definitions

The following definitions are provided for purpose of illustration andnot limitation.

As used herein, the term “fouling” generally refers to the accumulationof unwanted materials on the surfaces of processing equipment or thelike, particularly processing equipment in a hydrocarbon refiningprocess.

As used herein, the term “particulate-induced fouling” generally refersto fouling caused primarily by the presence of variable amounts oforganic or inorganic particulates. Organic particulates (such asprecipitated asphaltenes and coke particles) include, but are notlimited to, insoluble matter precipitated out of solution upon changesin process conditions (e.g., temperature, pressure, or concentrationchanges) or a change in the composition of the feed stream (e.g.,changes due to the occurrence of a chemical reaction). Inorganicparticulates include, but are not limited to, silica, iron oxide, ironsulfide, alkaline earth metal oxide, sodium chloride, calcium chlorideand other inorganic salts. One major source of these particulatesresults from incomplete solids removal during desalting and/or otherparticulate removing processes. Solids promote the fouling of crude oilsand blends due to physical effects by modifying the surface area of heattransfer equipment, allowing for longer holdup times at walltemperatures and causing coke formation from asphaltenes and/or crudeoil(s).

As used herein, the term “alkyl” refers to a monovalent hydrocarbongroup containing no double or triple bonds and arranged in a branched orstraight chain.

As used herein, the term “alkylene” refers to a divalent hydrocarbongroup containing no double or triple bonds and arranged in a branched orstraight chain.

As used herein, the term “alkenyl” refers to a monovalent hydrocarbongroup containing one or more double bonds and arranged in a branched orstraight chain.

As used herein, a “hydrocarbyl” group refers to any univalent radicalthat is derived from a hydrocarbon, including univalent alkyl, aryl andcycloalkyl groups.

As used herein, the term “crude hydrocarbon refinery component”generally refers to an apparatus or instrumentality of a process torefine crude hydrocarbons, such as an oil refinery process, which is, orcan be, susceptible to fouling. Crude hydrocarbon refinery componentsinclude, but are not limited to, heat transfer components such as a heatexchanger, a furnace, a crude preheater, a coker preheater, or any otherheaters, a FCC slurry bottom, a debutanizer exchanger/tower, otherfeed/effluent exchangers and furnace air preheaters in refineryfacilities, flare compressor components in refinery facilities and steamcracker/reformer tubes in petrochemical facilities. Crude hydrocarbonrefinery components can also include other instrumentalities in whichheat transfer can take place, such as a fractionation or distillationcolumn, a scrubber, a reactor, a liquid-jacketed tank, a pipestill, acoker and a visbreaker. It is understood that “crude hydrocarbonrefinery components,” as used herein, encompasses tubes, piping, bafflesand other process transport mechanisms that are internal to, at leastpartially constitute, and/or are in direct fluid communication with, anyone of the above-mentioned crude hydrocarbon refinery components.

As used herein, a reduction (or “reducing”) of particulate-inducedfouling is generally achieved when the ability of particulates to adhereto heated equipment surfaces is reduced, thereby mitigating their impacton the promotion of the fouling of crude oil(s), blends, and otherrefinery process streams.

As used herein, reference to a group being a particular polymer (e.g.,polypropylene or poly(ethylene-co-propylene) encompasses polymers thatcontain primarily the respective monomer along with negligible amountsof other substitutions and/or interruptions along polymer chain. Inother words, reference to a group being a polypropylene group does notrequire that the group consist of 100% propylene monomers without anylinking groups, substitutions, impurities or other substituents (e.g.,alkylene or alkenylene substituents). Such impurities or othersubstituents can be present in relatively minor amounts so long as theydo not affect the industrial performance of the additive, as compared tothe same additive containing the respective polymer substituent with100% purity.

For the purposes of the present application, when a polymer is referredto as comprising an olefin, the olefin present in the polymer is thepolymerized form of the olefin.

As used herein, a copolymer is a polymer comprising at least twodifferent monomer units (such as propylene and ethylene). A homo-polymeris a polymer comprising units of the same monomer (such as propylene). Apropylene polymer is a polymer having at least 50 mole % of propylene.

The term “vinyl termination”, also referred to as “allyl chain end(s)”or “vinyl content” is defined to be a polymer having at least oneterminus represented by:

where the “

” represents the polymer chain.

In a preferred embodiment the allyl chain end is represented by:

The amount of allyl chain ends (also called % vinyl termination) isdetermined using ¹H NMR at 120° C. using deuterated tetrachloroethane asthe solvent on a 500 MHz machine and in selected cases confirmed by ¹³CNMR. Resconi has reported proton and carbon assignments (neatperdeuterated tetrachloroethane used for proton spectra while a 50:50mixture of normal and perdcuterated tetrachlorocthane was used forcarbon spectra; all spectra were recorded at 100° C. on a Bruker AM 300spectrometer operating at 300 MHz for proton and 75.43 MHz for carbon)for vinyl terminated propylene polymers in J American Chemical Soc 1141992, 1025-1032, hereby incorporated by reference in its entirety, thatare useful herein.

“Isobutyl chain end” is defined to be a polymer having at least oneterminus represented by the formula:

where M represents the polymer chain. In an example embodiment, theisobutyl chain end is represented by one of the following formulae:

where M represents the polymer chain.

The “isobutyl chain end to allylic vinyl group ratio” is defined to bethe ratio of the percentage of isobutyl chain ends to the percentage ofallylic vinyl groups.

As used herein, the term “polymer” refers to a chain of monomers havinga Mn of 100 g/mol and above.

Reference will now be made to various aspects of the disclosed subjectmatter in view of the definitions above.

In one aspect, the additives of the disclosed subject matter caninteract with the materials in crude oils in a refinery or the like thatare prone to cause fouling, e.g., particulate impurities/contaminantsand asphaltenes. The interaction can be physical or chemical such asabsorption, association, or chemical bonding. The fouling materials canbe rendered more soluble in the crude oils as a result of interactionwith the antifouling additives, therefore the fouling on the exchangermetal surfaces can be reduced or eliminated.

In accordance with one aspect of the disclosed subject matter, a methodfor reducing fouling in a hydrocarbon refining process is provided. Themethod includes (i) providing a crude hydrocarbon for a refiningprocess; and (ii) adding an additive to the crude hydrocarbon, theadditive being represented by one of Formula A and Formula B below:

wherein in each of the Formula A and Formula B above:

m is an integer between 0 and 10 inclusive;

R₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenyl group;

R₂ is a C₁-C₄ branched or straight chained alkylene group;

R₃ is a C₁-C₄ branched or straight chained alkylene group;

R₃₁ is hydrogen or —R₈-R₉, wherein R₈ is C₁-C₄ branched or straightchained alkylene group, and R₉ is

wherein R₉₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup; or R₈ and R₉ together are a C₁-C₄ branched or straight chainedalkyl group optionally substituted with one or more amine groups; andfurther wherein the —N(R₃₁)—R₃— repeat unit is optionally interrupted inone or more places by a nitrogen-containing heterocyclic cycloalkylgroup; and

R₄ and R₅ are each independently selected from (a) hydrogen; (b) a bondconnected to R₃₁ in the last distal —N(R₃₁)—R₃— repeat unit; or (c)—R₆-R₇, wherein R₆ is C₁-C₄ branched or straight chained alkylene group,and R₇ is

wherein R₇₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup; wherein in Formula A, n is an integer between 0 and 10 inclusive,and the groups R₂′, R₃′, R₃₁′, R₄′ and R₅′ are each defined the same asR₂, R₃, R₃₁ and R₄, and R₅, respectively; and

wherein in Formula B, z is 1 or 2, and y is an integer between 1 and 5inclusive.

In certain embodiments, at least one of R₁, R₇₁, and R₉₁ of thecompounds shown above comprises polypropylene (PP), which can be atacticpolypropylene or isotactic polypropylene. The polypropylene can beamorphous, and can include isotactic or syndiotactic crystallizableunits. In some embodiments, the polypropylene includes meso diadsconstituting from about 30% to about 99.5% of the total diads of thepolypropylene. In alternative embodiments, at least one of R₁, R₇₁, andR₉₁ of the compounds above comprises polyethylene (PE).

In a further embodiment, at least one of R₁, R₇₁, and R₉₁ of thecompounds above comprises poly(ethylene-co-propylene) (EP). The molepercentage of the ethylene units and propylene units in thepoly(ethylene-co-propylene) can vary. For example, in some embodiments,the poly(ethylene-co-propylene) can contain about 1 to about 90 mole %of ethylene units and about 99 to about 10 mole % propylene units. Inother embodiments, the poly(ethylene-co-propylene) can contain about 10to about 90 mole % of ethylene units and about 90 to about 10 mole %propylene units. In certain embodiments, the poly(ethylene-co-propylene)contains about 10 to about 50 mole % of ethylene units.

In some embodiments of the above method, at least one of R₁, R₇₁, andR₉₁ of the additive of Formula I has a number-averaged molecular weightof from about 300 to about 30,000 g/mol (assuming one olefinunsaturation per chain, as measured by ¹H NMR). Alternatively, at leastone of R₁, R₇₁, and R₉₁ of the compounds above has a number-averagedmolecular weight (Mn) of from about 500 to 5,000 g/mol. In oneembodiment, the PP or EP included in the R₁, R₇₁ or R₉₁ of the compoundsabove, individually, has a molecular weight from about 300 to about30,000 g/mol (and as high as 60K or 60,000 g/mol.), or from about 500 toabout 5000 g/mol. In one embodiment, the PP or EP groups have amolecular weight, individually, ranging from about 500 to about 2500g/mol, or a molecular weight (Mn) of from about 500 to about 650 g/mol,or a molecular weight of from about 800 to about 1000 g/mol, or amolecular weight of from about 2000 to about 2500 g/mol.

In other embodiments of the compound, at least one of R₁, R₇₁, and R₉₁comprises poly(higher alpha-olefin) or poly(propylene-co-higheralpha-olefin), the higher alpha-olefin including two or more carbonatoms on each side chain. For example, suitable higher alpha-olefins caninclude, but are not limited to, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene and the like.

In certain embodiments of the above compound, the nitrogen content inthe compound of Formula I is about 1 wt % to about 10 wt % based on thetotal weight of the compound.

In certain embodiments, R₃ is —CH₂—CH₂—, and R₃₁ is hydrogen. In theseembodiments, the —N(R₃₁)—R₃— repeat unit can be interrupted in one ormore places by a 1,4-diethylenediamine.

With reference to Formula A, and in accordance with another aspect ofthe subject matter disclosed herein, a method for preparing a compoundfor reducing fouling in a hydrocarbon refining process is provided. Themethod includes:

(a) reacting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, with maleic anhydride to obtain a polymer represented by FormulaI below:

wherein R₂₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup;

(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)-R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)-R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

In certain embodiments of the above methods, the polymer base unit R₁₁has a number-averaged molecular weight of 300 to 30,000 g/mol (assumingone olefin unsaturation per chain, as measured by ¹H NMR), andalternatively, about 500 to 5,000 g/mol.

In some embodiments of the above methods, the polymer base unit R₁₁comprises polypropylene. The polypropylene can be either atacticpolypropylene or isotactic polypropylene. The polypropylene can beamorphous, and can include isotactic or syndiotactic crystallizableunits. In some embodiments, the polypropylene includes meso diadsconstituting from about 30% to about 99.5% of the total diads of thepolypropylene. The polymer base unit R₁₁ can also comprise polyethylene.

In alternative embodiments, the polymer base unit R₁₁ comprisespoly(ethylene-co-propylene). The poly(ethylene-co-propylene) can containfrom about 1 or 10 mole % to about 90 or 99 mole % of ethylene units andfrom about 99 or 90 mole % to about 10 or 1 mole % propylene units. Inone embodiment, the poly(ethylene-co-propylene) polymer contains fromabout 2 or 20 mole % to about 50 mole % ethylene units.

In one embodiment, the PP or EP included in R₁₁ to form Formula Iindividually has a number-averaged molecular weight (Mn) from about 300to about 30,000 g/mol, or from about 500 to about 5000 g/mol (assumingone olefin unsaturation per chain, as measured by ¹H NMR). In oneembodiment, the PP or EP groups have a molecular weight (Mn),individually, ranging from about 500 to about 2500 g/mol, or a molecularof from about 500 to about 650 g/mol, or a molecular weight of fromabout 800 to about 1000 g/mol, or a molecular weight of from about 2000to about 2500 g/mol.

In embodiments where the polymer base unit R₁₁ includes polypropylene orpoly(ethylene-co-propylene), such groups can be prepared, for example,by metallocene-catalyzed polymerization of propylene or a mixture ofethylene and propylene, which are then terminated with a high vinylgroup content in the chain end. The number-averaged molecular weight(M_(n)) of the PP or EP can be from about 300 to about 30,000 g/mol, asdetermined by ¹H NMR spectroscopy. The vinyl-terminated atactic orisotactic polypropylenes (v-PP) or vinyl-terminatedpoly(ethylene-co-propylene) (v-EP) suitable for further chemicalfunctionalization can have a molecular weight (M_(n)) approximately fromabout 300 to about 30,000 g/mol, and preferably about 500 to 5,000g/mol. The terminal olefin group can be a vinylidene group or an allylicvinyl group (both covered in Formula I). In certain embodiments, theterminal olefin group is an allylic vinyl group. In this regard, theterminal allylic vinyl group rich PP or EP as disclosed in U.S. Pat. No.8,372,930 and co-pending application U.S. Patent Application PublicationNo. 20090318646, can be used, which are both hereby incorporated byreference in their entirety. Some of the vinyl terminated EP or PPaccording to these co-pending applications contains more than 90% ofallylic terminal vinyl group.

In some embodiments of the above methods, R₁₁ can comprise propylene andless than 0.5 wt % comonomer, preferably 0 wt % comonomer, wherein theR₁₁ has:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 500 to about        20,000 g/mol, as measured by ¹H NMR, assuming one olefin        unsaturation per chain (preferably 500 to 15,000, preferably 700        to 10,000, preferably 800 to 8,000 g/mol, preferably 900 to        7,000, preferably 1000 to 6,000, preferably 1000 to 5,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0;    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

In some embodiments of the above methods, R₁₁ can comprise a propylenecopolymer having an Mn of 300 to 30,000 g/mol as measured by 1H NMR andassuming one olefin unsaturation per chain (preferably 400 to 20,000,preferably 500 to 15,000, preferably 600 to 12,000, preferably 800 to10,000, preferably 900 to 8,000, preferably 900 to 7,000 g/mol),comprising 10 to 90 mol % propylene (preferably 15 to 85 mol %,preferably 20 to 80 mol %, preferably 30 to 75 mol %, preferably 50 to90 mol %) and 10 to 90 mol % (preferably 85 to 15 mol %, preferably 20to 80 mol %, preferably 25 to 70 mol %, preferably 10 to 50 mol %) ofone or more alpha-olefin comonomers (preferably ethylene, butene,hexene, or octene, or decene, preferably ethylene), wherein the polymerhas at least X % allyl chain ends (relative to total unsaturations),where X is 80% or more, preferably 85% or more, preferably 90% or more,preferably 95% or more. Alternatively, R₁₁ can have at least 80%isobutyl chain ends (based upon the sum of isobutyl and n-propylsaturated chain ends), preferably at least 85% isobutyl chain ends,preferably at least 90% isobutyl chain ends. Alternately, R₁₁ can havean isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0,preferably 0.9:1 to 1.20:1.0, preferably 0.9:1.0 to 1.1:1.0.

In other embodiments, R₁₁ can comprise a polypropylene copolymer havingmore than 90 mol % propylene (preferably 95 to 99 mol %, preferably 98to 9 mol %) and less than 10 mol % ethylene (preferably 1 to 4 mol %,preferably 1 to 2 mol %), wherein the copolymer has:

at least 93% allyl chain ends (preferably at least 95%, preferably atleast 97%, preferably at least 98%);

a number average molecular weight (Mn) of about 400 to about 30,000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 500 to 20,000, preferably 600 to 15,000, preferably700 to 10,000 g/mol, preferably 800 to 9,000, preferably 900 to 8,000,preferably 1000 to 6,000);

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0,and

less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferablyless than 1000 ppm, preferably less than 500 ppm, preferably less than100 ppm).

In alternative embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably 60 to 90, preferably 70 to 90) mol % propyleneand from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol %ethylene, wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

an Mn of about 150 to about 20,000 g/mol, as measured by ¹H NMR andassuming one olefin unsaturation per chain (preferably 200 to 15,000,preferably 250 to 15,000, preferably 300 to 10,000, preferably 400 to9.500, preferably 500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.3:1.0,wherein monomers having four or more carbon atoms are present at from 0to 3 mol % (preferably at less than 1 mol %, preferably less than 0.5mol %, preferably at 0 mol %).

In further embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % C₄ to C₁₂ olefin (such as butene,hexene or octene, or decene, preferably butene), wherein the polymerhas:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 15,000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 200 to 12,000, preferably 250 to 10,000, preferably300 to 10,000, preferably 400 to 9500, preferably 500 to 9,000,preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0.

In certain embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % diene (such as C₄ to C₁₂ alpha-omegadienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene),wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 20,000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 200 to 15,000, preferably 250 to 12,000, preferably300 to 10,000, preferably 400 to 9.500, preferably 500 to 9,000,preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.

In other embodiments of the above methods, R₁₁ can comprise poly(higheralpha-olefin) or poly(propylene-co-higher alpha-olefin), the higheralpha-olefin including two or more carbon atoms on each side chain. Forexample, suitable higher alpha-olefins can include, but are not limitedto, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-hexadecene, 1-octadecene and the like.

In certain embodiments, R₁₁ includes those vinyl terminatedmacromonomers disclosed in U.S. Patent Application Publication Nos.20120245312, 20120245310. 20120245311, 20120245313, and U.S. ProvisionalApplication No. 61/704,604, the disclosure of each of which isincorporated by reference in its entirety herein.

In the above method of preparation, maleic anhydride can be used for thereaction of converting a polymer base unit R₁₁ having a terminal vinylfunctionality to a compound of Formula I. The reaction can proceedthrough a thermal condition (e.g., at temperature of about 150° C. to260° C.) without using external radical providers, such as a peroxideinitiator. Under this condition, a compound of Formula I can beobtained, along with a polymer having a mono-succinic anhydride terminalgroup. For example and as embodied herein, the thermal reaction betweenR₁₁ and maleic anhydride can be illustrated below in Scheme 1 using avinyl terminated polypropylene as an example of R₁₁.

The above reaction can be carried out without the use of any solvent.Alternatively, any inert solvent (e.g., paraffinic solvent, naphthenicsolvent, aromatic solvent, halogenated solvent, mineral oil, syntheticfluid, etc.) with appropriate boiling point or boiling point range canbe used. The reaction can be conducted in an open system underatmospheric pressure by using standard laboratory glassware or in aclosed system by using an autoclave (or any sealed vessel suitable forholding the pressure). A catalyst can also be used to increase the rateof reaction between the hydrocarbon copolymer and the unsaturatedcarboxylic acid derivative.

The vinyl terminated polymer can also be a copolymer of polypropylene,for example, poly-ethylene-propylene, or poly-propylene-higheralpha-olefin. In such cases, the reactions under a thermal condition canbe illustrated below in Scheme 2 and Scheme 3, respectively.

The above reactions can be performed at temperatures between about 150°C. to about 260° C. and between about atmospheric pressure to about 500psi. The reaction can be conducted in an open system under atmosphericpressure by using standard laboratory glassware or in a closed system byusing an autoclave (or any sealed vessel suitable for maintainingpressure). Reaction time can vary from minutes to hours depending on theconditions used. The rate of reaction will increase with increasedtemperature and pressure. At temperatures between about 220-260° C. atelevated pressure, high conversion of the vinyl-terminated polymers canbe achieved within about two hours.

The charge ratio of vinyl-terminated polymers to maleic anhydride in thereactions depicted in Scheme 1, Scheme 2 and Scheme 3 can vary fromabout 1:1 to about 1:10, or preferably from about 1:1 to about 1:6, orpreferably from about 1:1 to about 1:4, or preferably from about 1:1 toabout 1:3, or preferably from about 1:1 to about 1:2, or preferably fromabout 1:1 to about 1:1.5, or preferably from about 1:1 to about 1:1.2.Increasing the charge ratio of maleic anhydride to vinyl-terminatedpolymer will increase the proportion of di-succinic anhydride productand decrease the proportion of mono-succinic anhydride product.Additionally, at a given temperature, increasing the reaction time willincrease the proportion of di-succinic anhydride reaction productsrelative to mono-succinic anhydride products, provided that sufficientmaleic anhydride is present in the reaction system. [0074]1 The methodof preparing the compound of Formula A can include reacting the succinicanhydride-containing polymers obtained above with a polyamine (PAM). Thereaction can proceed through a condensation mechanism. The polyamine caninclude linear, branched or cyclic isomers of an oligomer ofethyleneamine, or mixtures thereof, wherein each two neighboringnitrogens in the oligomer of ethyleneamine are bridged by one or twoethyleneamine groups. For example, the polyamine can be selected frompolyethyleneamines with general molecular formula H₂N(CH₂CH₂NH)_(x)H(where x=1, 2, 3, . . . ) such as ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,hexaethyleneheptamine, and mixtures thereof. In some embodiments, thepolyamine can comprise a heavy polyamine, such as polyethyleneamineheavy bottoms available from Dow Chemical as “Heavy Polyamine X” orHPA-X.

Using a reaction between the products of Scheme 3 andtetraethylenepentamine as an example of PAM, the condensation reactioncan be illustrated below in Scheme 4.

In additional embodiments of the disclosed subject matter, nucleophilicreagents other than polyamines can be used to functionalize thecompounds of Formula I. These reagents include, for example, monoamines,diamines, amino alcohols, polyetheramines, polyols, polyalkyleneglycols, polyalkylene polyamine and the like.

Furthermore, vinylidene-terminated polymer or copolymer (e.g.,ethylene-propylene copolymer, and propylene-higher alpha-olefincopolymer) can also be used as R₁₁. Illustrations for usingvinylidene-terminated polypropylene and vinyl idene-terminatedpropylene-higher alpha-olefin copolymer as R₁₁ are shown below in Scheme5 and Scheme 6, respectively.

As a result of the amination reactions, the number of polymer chainattached to each polyamine molecule can vary from one to two to three ormore. In addition, both primary and secondary amino groups on thepolyamine can participate in the reaction with theanhydride-functionalized polymer. Other commercially available lower orhigher polyamines with linear, branched, cyclic or heterocyclicstructures can also be used. It is well-known and understood by thoseskilled in the art that these polyamines can be mixtures of compoundscomprised of molecules with a distribution of chain lengths, differentlevel and type of amine (primary, secondary, and tertiary) functionalgroups, and varying degree of linear, branched and cyclic structures.For example, possible isomers for tetracthylenepentamine include thefollowing:

As the molecular weight of polyamines increases, the number of possibleisomers increases as well.

In a further aspect, a method for preparing a compound according toFormula B for treating an emulsion of crude hydrocarbon and/or reducingfouling in a hydrocarbon refining process is provided. The methodincludes:

(a) reacting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, with maleic anhydride in the presence of a radical initiator toobtain a polymer represented by Formula II below:

wherein R₂₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, z is 1 or 2, and y is an integer between 1 and 5 inclusive;

(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)-R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)-R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

In certain embodiments of the above methods, the polymer base unit R₁₁has a number-averaged molecular weight of 300 to 30,000 g/mol (assumingone olefin unsaturation per chain, as measured by ¹H NMR), andalternatively, about 500 to 5,000 g/mol.

In some embodiments of the above methods, the polymer base unit R₁₁comprises polypropylene. The polypropylene can be either atacticpolypropylene or isotactic polypropylene. The polypropylene can beamorphous, and can include isotactic or syndiotactic crystallizableunits. In some embodiments, the polypropylene includes meso diadsconstituting from about 30% to about 99.5% of the total diads of thepolypropylene. The polymer base unit R₁₁ can also comprise polyethylene.

In alternative embodiments, the polymer base unit R₁₁ comprisespoly(ethylene-co-propylene). The poly(ethylene-co-propylene) can containfrom about 1 or 10 mole % to about 90 or 99 mole % of ethylene units andfrom about 99 or 90 mole % to about 10 or 1 mole % propylene units. Inone embodiment, the poly(ethylene-co-propylene) polymer contains fromabout 2 or 20 mole % to about 50 mole % ethylene units.

In one embodiment, the PP or EP included in the R₁₁ to form Formula IIindividually has a number-averaged molecular weight (M_(n)) from about300 to about 30,000 g/mol, or from about 500 to about 5000 g/mol(assuming one olefin unsaturation per chain, as measured by ¹H NMR). Inone embodiment, the PP or EP groups have a molecular weight,individually, ranging from about 500 to about 2500 g/mol, or a molecularof from about 500 to about 650 g/mol, or a molecular weight of fromabout 800 to about 1000 g/mol, or a molecular weight of from about 2000to about 2500 g/mol.

In embodiments where the polymer base unit R₁₁ include polypropylene orpoly(ethylene-co-propylene), such groups can be prepared, for example,by metallocene-catalyzed polymerization of propylene or a mixture ofethylene and propylene, which are then terminated with a high vinylgroup content in the chain end. The number-averaged molecular weight(M_(n)) of the PP or EP can be from about 300 to about 30,000 g/mol, asdetermined by ¹H NMR spectroscopy. The vinyl-terminated atactic orisotactic polypropylenes (v-PP) or vinyl-terminatedpoly(ethylene-co-propylene) (v-EP) suitable for further chemicalfunctionalization can have a molecular weight (M_(n)) approximately fromabout 300 to about 30,000 g/mol, and preferably about 500 to 5,000g/mol. The terminal olefin group can be a vinylidene group or an allylicvinyl group. In certain embodiments, the terminal olefin group is anallylic vinyl group. In this regard, the terminal allylic vinyl grouprich PP or EP as disclosed in U.S. Pat. No. 8,372,930 and co-pendingapplication, U.S. Patent Application Publication No. 20090318646, can beused, each of which is hereby incorporated by reference in its entirety.Some of the vinyl terminated EP or PP according to these co-pendingapplications contains more than 90% of allylic terminal vinyl group.

In some embodiments of the above methods, R₁₁ can comprise propylene andless than 0.5 wt % comonomer, preferably 0 wt % comonomer, wherein theR₁₁ has:

-   -   i) at least 93% allyl chain ends (preferably at least 95%,        preferably at least 97%, preferably at least 98%);    -   ii) a number average molecular weight (Mn) of about 500 to about        20,000 g/mol, as measured by ¹H NMR, assuming one olefin        unsaturation per chain (preferably 500 to 15,000, preferably 700        to 10,000, preferably 800 to 8,000 g/mol, preferably 900 to        7,000, preferably 1000 to 6,000, preferably 1000 to 5,000);    -   iii) an isobutyl chain end to allylic vinyl group ratio of 0.8:1        to 1.3:1.0;    -   iv) less than 1400 ppm aluminum, (preferably less than 1200 ppm,        preferably less than 1000 ppm, preferably less than 500 ppm,        preferably less than 100 ppm).

In some embodiments of the above methods, R₁₁ can comprise a propylenecopolymer having an Mn of 300 to 30,000 g/mol as measured by 1H NMR andassuming one olefin unsaturation per chain (preferably 400 to 20,000,preferably 500 to 15,000, preferably 600 to 12,000, preferably 800 to10,000, preferably 900 to 8,000, preferably 900 to 7,000 g/mol),comprising 10 to 90 mol % propylene (preferably 15 to 85 mol %,preferably 20 to 80 mol %, preferably 30 to 75 mol %, preferably 50 to90 mol %) and 10 to 90 mol % (preferably 85 to 15 mol %, preferably 20to 80 mol %, preferably 25 to 70 mol %, preferably 10 to 50 mol %) ofone or more alpha-olefin comonomers (preferably ethylene, butene,hexene, or octene, or decene, preferably ethylene), wherein the polymerhas at least X % allyl chain ends (relative to total unsaturations),where X is 80% or more, preferably 85% or more, preferably 90% or more,preferably 95% or more. Alternatively, R₁₁ can have at least 80%isobutyl chain ends (based upon the sum of isobutyl and n-propylsaturated chain ends), preferably at least 85% isobutyl chain ends,preferably at least 90% isobutyl chain ends. Alternately, R₁₁ can havean isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0,preferably 0.9:1 to 1.20:1.0, preferably 0.9:1.0 to 1.1:1.0.

In other embodiments, R₁₁ can comprise a polypropylene copolymer havingmore than 90 mol % propylene (preferably 95 to 99 mol %, preferably 98to 9 mol %) and less than 10 mol % ethylene (preferably 1 to 4 mol %,preferably 1 to 2 mol %), wherein the copolymer has:

at least 93% allyl chain ends (preferably at least 95%, preferably atleast 97%, preferably at least 98%);

a number average molecular weight (Mn) of about 400 to about 30,000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 500 to 20,000, preferably 600 to 15,000, preferably700 to 10,000 g/mol, preferably 800 to 9,000, preferably 900 to 8,000,preferably 1000 to 6,000);

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0,and

less than 1400 ppm aluminum, (preferably less than 1200 ppm, preferablyless than 1000 ppm, preferably less than 500 ppm, preferably less than100 ppm).

In alternative embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably 60 to 90, preferably 70 to 90) mol % propyleneand from 10 to 50 (preferably 10 to 40, preferably 10 to 30) mol %ethylene, wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%):

an Mn of about 150 to about 20,000 g/mol, as measured by ¹H NMR andassuming one olefin unsaturation per chain (preferably 200 to 15,000,preferably 250 to 15,000, preferably 300 to 10,000, preferably 400 to9,500, preferably 500 to 9,000, preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.3:1.0,wherein monomers having four or more carbon atoms are present at from 0to 3 mol % (preferably at less than 1 mol %, preferably less than 0.5mol %, preferably at 0 mol %).

In further embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % C₄ to C₁₂ olefin (such as butene,hexene or octene, or decene, preferably butene), wherein the polymerhas:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 15,000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 200 to 12,000, preferably 250 to 10,000, preferably300 to 10,000, preferably 400 to 9500, preferably 500 to 9,000,preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.8:1 to 1.35:1.0.

In certain embodiments, R₁₁ can comprise a polypropylene copolymercomprising:

at least 50 (preferably at least 60, preferably 70 to 99.5, preferably80 to 99, preferably 90 to 98.5) mol % propylene, from 0.1 to 45(preferably at least 35, preferably 0.5 to 30, preferably 1 to 20,preferably 1.5 to 10) mol % ethylene, and from 0.1 to 5 (preferably 0.5to 3, preferably 0.5 to 1) mol % diene (such as C₄ to C₁₂ alpha-omegadienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, and dicyclopentadiene),wherein the polymer has:

at least 90% allyl chain ends (preferably at least 91%, preferably atleast 93%, preferably at least 95%, preferably at least 98%);

a number average molecular weight (Mn) of about 150 to about 20.000g/mol, as measured by ¹H NMR and assuming one olefin unsaturation perchain (preferably 200 to 15,000, preferably 250 to 12,000, preferably300 to 10,000, preferably 400 to 9.500, preferably 500 to 9,000,preferably 750 to 9,000); and

an isobutyl chain end to allylic vinyl group ratio of 0.7:1 to 1.35:1.0.

In other embodiments of the above methods, R₁₁ can comprise poly(higheralpha-olefin) or poly(propylene-co-higher alpha-olefin), the higheralpha-olefin including two or more carbon atoms on each side chain. Forexample, suitable higher alpha-olefins can include, but are not limitedto, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-hexadecene, 1-octadecene and the like.

In certain embodiments, R₁₁ includes those vinyl terminatedmacromonomers disclosed in U.S. Patent Application Publication Nos.20120245312, 20120245310, 20120245311, 20120245313, and U.S. ProvisionalApplication No. 61/704,604, the disclosure of each of which isincorporated by reference in its entirety herein.

In the disclosed method of preparation of compound of Formula B, maleicanhydride can be used for the reaction of converting a polymer base unitR₁₁ having a terminal vinyl functionality to a compound of Formula II.The reaction between R₁₁ and maleic anhydride can be initiated by aperoxide initiator which provides a radical species. The reaction underthis condition can result in Formula II noted above, as illustratedbelow in Scheme 7:

The vinyl-terminated polymer and maleic anhydride can be mixed eitherneat or in an inert solvent (e.g., paraffinic solvent, naphthenicsolvent, aromatic solvent, halogenated solvent, mineral oil, syntheticfluid, etc.) with appropriate boiling point or boiling point range. Thereaction can be conducted in an open system under atmospheric pressureby using standard laboratory glassware or in a closed system by using anautoclave (or any sealed vessel suitable for holding the pressure). Thetemperature can vary from 80 to 180° C., or preferably from 100 to 170°C., or preferably from 120 to 170° C., or preferably from 130 to 170° C.Reactant charge ratio of vinyl-terminated polymer to maleic anhydridecan vary from about 1:1 to about 1:4, or from about 1:1 to about 1:3, orfrom about 1:1 to about 1:2, or from about 1:1 to about 1:1.5, or fromabout 1:1 to about 1:1.2. Suitable radical initiators include, but notlimited to, organic peroxides such as di-tert-butyl peroxide, dicumylperoxide, lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide,cumene hydroperoxide, tert-butyl peroxybenzoate (peroxy ester),tert-butyl peracetate (peroxy ester), 2,2′-azobisisobutyronitrile(AIBN), 1,1′-azobis(cyclohexanecarbonitrile) or similar diazo compounds.The radical initiator can be introduced in portions over a convenientperiod of time, if desired for controlling reaction rate, to the mixtureof vinyl-terminated polymer and maleic anhydride at a suitabletemperature (e.g., from about 120 to 165° C. for di-tert-butyl peroxide)needed for thermal decomposition of the radical initiator to generateradical species at a rate suitable for the reaction.

As previously noted, the method of preparing the compounds can includereacting the succinic anhydride-containing polymers obtained above witha polyamine. The reaction can proceed through a condensation mechanism.The polyamine can include linear, branched or cyclic isomers of anoligomer of ethyleneamine, or mixtures thereof, wherein each twoneighboring nitrogens in the oligomer of ethyleneamine are bridged byone or two ethyleneamine groups. For example, the polyamine can beselected from polyethyleneamines with general molecular formulaH₂N(CH₂CH₂NH)_(x)H (where x=1, 2, 3, . . . ) such as ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, hexaethyleneheptamine, and mixtures thereof. Insome embodiments, the polyamine can comprise a heavy polyamine, such aspolyethyleneamine heavy bottoms available from Dow Chemical as “HeavyPolyamine X” or HPA-X.

Using a reaction between the products of Scheme 7 andtetraethylenepentamine as an exemplary polyamine, the condensationreaction can be illustrated below in Scheme 8.

In alternative embodiments, nucleophilic reagents other than polyaminescan be used to functionalize the compounds of Formula II. These reagentsinclude, for example, monoamines, diamines, amino alcohols,polyetheramines, polyols, polyalkylene glycols, polyalkylene polyamineand the like.

Furthermore, vinylidene-terminated polymer or copolymer (e.g.,ethylene-propylene copolymer, and propylene-higher alpha-olefincopolymer) can also be used as R₁₁. Illustrations for usingvinylidene-terminated polypropylene and vinylidene-terminatedpropylene-higher alpha-olefin copolymer as R₁₁ are shown below in Scheme9 and Scheme 10, respectively.

As a result of the amination reactions, the number of polymer chainattached to each polyamine molecule can vary from one to two to three ormore. In addition, both primary and secondary amino groups on thepolyamine can participate in the reaction with theanhydride-functionalized polymer. Other commercially available lower orhigher polyamines with linear, branched, cyclic or heterocyclicstructures can also be used. It is well-known and understood by thoseskilled in the art that these polyamines can be mixtures of compoundscomprised of molecules with a distribution of chain lengths, differentlevel and type of amine (primary, secondary, and tertiary) functionalgroups, and varying degree of linear, branched and cyclic structures.For example, possible isomers for tetraethylenepentamine include thefollowing:

As the molecular weight of polyamines increases, the number of possibleisomers increases as well.

In another aspect of the disclosed subject matter, compounds (additives)prepared by the method discussed above and various embodiments thereofare provided.

In another aspect, a method for reducing fouling in a hydrocarbonrefining process is provided, which comprises providing a crudehydrocarbon for a refining process, and adding to the crude hydrocarbonan additive of Formula A or Formula B or various embodiments thereof asdescribed above (e.g., at standard operation conditions).

Another aspect of the disclosed subject matter provides a system forrefining hydrocarbons that includes at least one crude hydrocarbonrefinery component, in which the crude hydrocarbon refinery componentincludes an additive selected from any one of the additives describedherein. The crude hydrocarbon refining component can be selected from aheat exchanger, a furnace, a crude preheater, a coker preheater, a FCCslurry bottom, a debutanizer exchanger, a debutanizer tower, afeed/effluent exchanger, a furnace air preheater, a flare compressorcomponent, a steam cracker, a steam reformer, a distillation column, afractionation column, a scrubber, a reactor, a liquid-jacketed tank, apipestill, a coker, and a visbreaker. For example, the crude hydrocarbonrefining component can be a heat exchanger (e.g., a crude pre-heat trainheat exchanger). Such methods and systems are described in greaterdetails in the following sections and examples.

Another aspect of the disclosed subject matter provides a compositionfor reducing fouling that includes at least one of any of theabove-described additives, and a boronating agent. The boronating agentcan be any one or more compounds selected from boric acid, anortho-borate, or a meta-borate, for example, boric acid, trimethylmetaborate (trimethoxyboroxine), triethyl metaborate, tributylmetaborate, trimethyl borate, triethylborate, triisopropyl borate(triisopropoxyborane), tributyl borate (tributoxyborane) and tri-t-butylborate. Other boronating agents can be used, such as those disclosed inco-pending applications US20100038290 and US20100170829, eachincorporated by reference herein in its entirety.

As disclosed in U.S. Patent Publication No. 20100170829, incorporatedherein by reference in its entirety, monosuccinic anhydride compoundswhich are also suitable for use as antifouling additives can be formedby the methods described above, or, with reference to the method ofsynthesizing Formula A, by providing heat and not a radical initiatorduring the reaction of the polymer base unit and the anhydride.

Further Compositions for Reducing Fouling

The additives of the disclosed subject matter can be used incompositions that prevent fouling, including particulate-inducedfouling. In addition to the additives of the disclosed subject matter,the compositions can further contain a hydrophobic oil solubilizer forthe additive and/or a dispersant for the additive.

Suitable solubilizers can include, for example, surfactants, carboxylicacid solubilizers, such as the nitrogen-containing phosphorous-freecarboxylic solubilizers disclosed in U.S. Pat. No. 4,368,133, herebyincorporated by reference in its entirety.

Also as disclosed in U.S. Pat. No. 4,368,133, hereby incorporated byreference in its entirety, surfactants that can be included incompositions of the disclosed subject matter can include, for example,cationic, anionic, nonionic or amphoteric type of surfactant. See, forexample. McCutcheon's “Detergents and Emulsifiers”, 1978, North AmericanEdition, published by McCutcheon's Division, MC Publishing Corporation,Glen Rock, N.J., U.S.A., including pages 17-33, which is herebyincorporated by reference in its entirety.

The compositions of the disclosed subject matter can further include,for example, viscosity index improvers, anti-foamants, antiwear agents,demulsifiers, anti-oxidants, and other corrosion inhibitors.

Furthermore, the additives of the disclosed subject matter can be addedwith other compatible components that address other problems that canpresent themselves in an oil refining process known to one of ordinaryskill in the art.

Uses of the Additives and Compositions for Antifouling Applications

The additives of the disclosed subject matter are generally soluble in atypical hydrocarbon refinery stream and can thus be added directly tothe process stream, alone or in combination with other additives thateither reduce fouling or improve some other process parameter.

The additives can be introduced, for example, upstream from theparticular crude hydrocarbon refinery component(s) (e.g., a heatexchanger) in which it is desired to prevent fouling (e.g.particulate-induced fouling). Alternatively, the additive can be addedto the crude oil prior to being introduced to the refining process, orat the very beginning of the refining process.

It is noted that water can have a negative impact on boron-containingadditives. Accordingly, it is advisable to add boron-containingadditives at process locations that have a minimal amount of water.

While not limited thereto, the additives of the disclosed subject matterare particularly suitable in reducing or preventing particulate-inducedfouling. Thus one aspect of the disclosed subject matter provides amethod of reducing and/or preventing, in particular, particulate-inducedfouling that includes adding at least one additive of the disclosedsubject matter to a process stream that is known, or believed tocontribute to, particulate-induced fouling. To facilitate determinationof proper injection points, measurements can be taken to ascertain theparticulate level in the process stream. Thus, one embodiment of thedisclosed subject matter includes identifying particular areas of arefining process that have relatively high particulate levels, andadding any one of the additives of the disclosed subject matter in closeproximity to these areas (e.g., just upstream to the area identified ashaving high particulate levels).

In some embodiments of the disclosed subject matter, a method to reducefouling is provided comprising adding any one of the above-mentionedadditives or compositions to a crude hydrocarbon refinery component thatis in fluid communication with a process stream that contains, at least50 wppm of particulates, including organic and inorganic particulates.In another embodiment of the disclosed subject matter, a method toreduce fouling is provided comprising adding any one of theabove-mentioned antifouling additives or compositions to a crudehydrocarbon refinery component that is in fluid communication with aprocess stream. In another embodiment of the disclosed subject matter, amethod to reduce fouling is provided comprising adding any one of theabove-mentioned additives to a crude hydrocarbon refinery component thatis in fluid communication with a process stream that contains at least250 wppm (or 1000 wppm, or 10,000 wppm) of particulates, includingorganic and inorganic particulates, as defined above.

In some embodiments of the disclosed subject matter, the additives orcompositions of the disclosed subject matter are added to selected crudeoil process streams known to contain, or possibly contain, problematicamounts of organic or inorganic particulate matter (e.g. 1-10,000 wppm),such as inorganic salts. Accordingly, the additives of the disclosedsubject matter can be introduced far upstream, where the stream isrelatively unrefined (e.g. the refinery crude pre-heat train). Theadditives can be also added, for example, after the desalter tocounteract the effects of incomplete salt removal or to the bottoms exitstream from the fractionation column to counteract the high temperaturesthat are conducive to fouling.

FIG. 1 demonstrates possible additive injection points within therefinery crude pre-heat train for the additives of the disclosed subjectmatter, wherein the numbered circles represent heat exchangers. As shownin FIG. 1, the additives can be introduced in crude storage tanks and atseveral locations in the preheat train. This includes at the crudecharge pump (at the very beginning of the crude pre-heat train), and/orbefore and after the desalter, and/or to the bottoms stream from a flashdrum.

The total amount of additive to be added to the process stream can bedetermined by a person of ordinary skill in the art. In one embodiment,up to about 1000 wppm of additive is added to the process stream. Forexample, the additive can be added such that its concentration, uponaddition, is about 50 ppm, 250 ppm or 500 ppm. More or less additive canbe added depending on, for example, the amount of particulate in thestream, the ΔT associated with the particular process and the degree offouling reduction desired in view of the cost of the additive.

The additives or compositions of the disclosed subject matter can beadded in a solid (e.g. powder or granules) or liquid form directly tothe process stream. As mentioned above, the additives or compositionscan be added alone, or combined with other components to form acomposition for reducing fouling (e.g. particulate-induced fouling). Anysuitable technique can be used for adding the additive to the processstream, as known by a person of ordinary skill in the art in view of theprocess to which it is employed. As a non-limiting example, theadditives or compositions can be introduced via injection that allowsfor sufficient mixing of the additive and the process stream.

EXAMPLES

The disclosed subject matter is further described by means of theexamples, presented below. The use of such examples is illustrative onlyand in no way limits the scope and meaning of the disclosed subjectmatter or of any exemplified term. Likewise, the disclosed subjectmatter is not limited to any particular preferred embodiments describedherein. Indeed, many modifications and variations of the disclosedembodiments will be apparent to those skilled in the art upon readingthis specification.

Example 1 Synthesis of Compounds

Various examples of using the methods of compound synthesis describedabove are provided herein. Polyisobutylene succinimide dispersants wereobtained from commercial suppliers (Infineum, Lubrizol, Chevron Oronite,Afton Chemical, BASF, etc). Alternatively, polyisobutylene-basedpolyamine succinimide dispersants were prepared by using commerciallyavailable highly reactive polyisobutylenes (HR-PIB) from BASF and fromTexas Petrochemcials (TPC) as exemplified below.

Example 1A Maleation of Vinylidene-Terminated Polyisobutylene (PIB) withMaleic Anhydride

To a 300 ml stainless steel autoclave equipped with a mechanical stirrerand an N₂ inlet and an N₂ outlet was added highly reactivepolyisobutylene (BASF Glissopal 2300, 85 g) followed by maleic anhydride(15.65 g, 159.6 mmol) at room temperature. The mixture was stirred andflushed three times with nitrogen at room temperature and pressurized to80 psi. The mixture was heated to 250° C. for 2 hours and allowed tocool to room temperature. The pressure was released slowly and theautoclave was opened. The mixture was diluted with hexanes, filteredunder house vacuum and the filtrate was concentrated on a rotaryevaporator. The mixture was heated at 95° C. under high vacuum to afforda viscous light brown oily product (90.66 g). Elemental analyses forthis PIB-SA material found C: 82.44%, H: 13.25%. The oxygen content ofthis material is estimated to be about 4.31 wt % by difference. Theanhydride content of this polymer material is estimated to be about0.898 mmol/g. Based on the molecular weight of polymer startingmaterial, there is an average of 2.10 succinic anhydride functionalityper polymer chain.

Example 1B Maleation of Vinyl-Terminated Polypropylene (Vt-PP) withMaleic Anhydride

A mixture of vinyl-terminated polypropylene (¹H NMR Mn 1210 g/mol, 44.00g) and maleic anhydride (10.70 g, 109.1 mmol) was heated at 205° C. for24 hours under a nitrogen atmosphere. The mixture was cooled to roomtemperature, diluted with hexanes, filtered and concentrated on a rotaryevaporator. Excess maleic anhydride was removed by heating under highvacuum to afford a viscous brown oily product (46.59 g). Elementalanalyses for this PP-SA material found C: 81.27%, H: 13.19%. The oxygencontent of this material is estimated to be about 5.54 wt % bydifference. The anhydride content of this polymer material is estimatedto be about 1.154 mmol/g. Based on the molecular weight of polymerstarting material, there is an average of 1.55 succinic anhydridefunctionality per polymer chain.

Example 1C Maleation of Vinyl-Terminated Propylene/1-Hexene Copolymerwith Maleic Anhydride

A mixture of vinyl-terminated propylene/1-hexene copolymer (¹H NMR Mn1638 g/mol, 48.60 g) and maleic anhydride (11.64 g, 118.7 mmol) washeated at 190° C. for 42 hours under a nitrogen atmosphere. The mixturewas cooled to room temperature, diluted with hexanes, filtered andconcentrated on a rotary evaporator. Excess maleic anhydride was removedby heating under high vacuum to afford a viscous brown oily product(53.10 g). Elemental analyses for this C₃C₆-SA material found C: 82.33%,H: 13.26%. The oxygen content of this material is estimated to be about4.41 wt % by difference. The anhydride content of this polymer materialis estimated to be about 0.919 mmol/g. Based on the molecular weight ofpolymer starting material, there is an average of 1.66 succinicanhydride functionality per polymer chain.

Example 1D Condensation of Polyisobutylene Succinic Anhydride (PIB-SA)with Tetraethylenepentamine (TEPA)

A mixture of polyisobutylene succinic anhydride from Example 1A (25.00g, 22.45 mmol anhydride) and xylenes (100 ml) was stirred at roomtemperature under a nitrogen atmosphere and a solution oftetraethylenepentamine (2.36 g, 12.47 mmol) in xylenes (15 ml) wasslowly added. The resulting mixture was heated in an oil bath at 165° C.for 15.5 hours. The brown mixture was cooled to room temperature andexcess xylenes removed on a rotary evaporator. The residual liquidproduct was further purified by heating under high vacuum to afford aviscous brown oily product (26.91 g). Elemental analyses for thisPIB-SA-TEPA compound found C: 81.32%, H: 13.25%. N: 3.05%.

Example 1E Condensation of Polypropylene Succinic Anhydride (PP-SA) withTetraethylenepentamine (TEPA)

A mixture of polypropylene succinic anhydride from Example 1B (18.00 g,20.77 mmol anhydride) and xylenes (50 ml) was stirred at roomtemperature under a nitrogen atmosphere and a solution oftetraethylenepentamine (3.15 g, 16.6 mmol) in xylenes (10 ml) was slowlyadded. The resulting mixture was heated in an oil bath at 175° C. for 24hours. The brown mixture was cooled to room temperature and excessxylenes removed on a rotary evaporator. The residual liquid product wasfurther purified by heating under high vacuum to afford a viscous brownoily product (20.52 g). Elemental analyses for this PP-SA-TEPA materialfound C: 78.30%, H: 12.97%, N: 5.11%.

Example 1F Condensation of Propylene/1-Hexene Succinic Anhydride(C₃C₆-SA) with Tetraethylenepentamine (TEPA)

A mixture of propylene/1-hexene succinic anhydride Example 1C (25.70 g,23.62 mmol anhydride) and xylenes (60 ml) was stirred at roomtemperature under a nitrogen atmosphere and a solution oftetraethylenepentamine (2.55 g, 13.5 mmol) in xylenes (15 ml) was slowlyadded. The resulting mixture was heated in an oil bath at 170° C. for 24hours. The brown mixture was cooled to room temperature and excessxylenes removed on a rotary evaporator. The residual liquid product wasfurther purified by heating under high vacuum to afford a viscous brownoily product (27.58 g). Elemental analyses for this C₃C₆-SA-TEPAmaterial found C: 81.38%, H: 12.74%, N: 3.30%.

Example 1G Maleation of Vinyl-Terminated Atactic Polypropylene

To a two-neck 500 ml round-bottomed flask equipped with an N₂ inlet andan N₂ outlet was added vinyl-terminated atactic polypropylene (GPC M_(w)5646, M_(n) 1474, ¹H NMR Mn 1190.19 g/mol, 75.00 g, 63.02 mmol) followedby maleic anhydride (15.45 g, 157.56 mmol) at room temperature. Themixture was flushed with nitrogen for 10 min at room temperature and themixture was heated to 190° C. (oil bath) for 63.5 hours under a nitrogenatmosphere. Additional maleic anhydride (3.10 g, 31.61 mmol) was addedto the mixture that had been cooled to about 120° C. and heating wascontinued at 190° C. (oil bath) for an additional 17 hours under anitrogen atmosphere. The mixture was cooled to room temperature, dilutedwith hexanes, filtered and concentrated on a rotary evaporator. Excessmaleic anhydride was removed by heating at 95-100° C. under high vacuumto afford a light brown viscous oily product (85.70 g). GPC M_(w) 4020,M_(n) 1413. Elemental analyses for this polypropylene succinic anhydridefound C: 80.79%. H: 12.51%. The oxygen content of this material isestimated to be about 6.70 wt % by difference. The anhydride content ofthis polymer material is estimated to be about 1.396 mmol/g. Based onthe molecular weight of polymer starting material, there is an averageof 1.93 succinic anhydride functionality per polymer chain.

Example 1H Maleation of Vinyl-Terminated Atactic Polypropylene

To a 300 ml stainless steel autoclave equipped with a mechanical stirrerand an N₂ inlet and a N₂ outlet was added vinyl-terminated atacticpolypropylene (GPC M_(w) 2387, M_(n) 1069, ¹H NMR Mn 1015.76 g/mol, 90g, 88.60 mmol) followed by maleic anhydride (34.75 g, 354.37 mmol) atroom temperature. The mixture was stirred and flushed three times withnitrogen at room temperature and pressurized to about 250 psi withnitrogen. The mixture was heated to 250° C. for 3 hours at about 400 psiand allowed to cool to room temperature. The pressure was releasedslowly and the autoclave was opened. The mixture was diluted withhexanes, filtered under house vacuum and the filtrate was concentratedon a rotary evaporator. Excess maleic anhydride was removed by heatingat 95° C. under high vacuum to afford a light brown viscous oily product(100.92 g). GPC M_(w) 2527, M_(n) 1112. Elemental analyses for thispolypropylene succinic anhydride found C: 77.92%, H: 11.77%. The oxygencontent of this material is estimated to be about 10.31 wt % bydifference. The anhydride content of this copolymer material isestimated to be about 2.148 mmol/g. Based on the molecular weight ofpolymer starting material, there is an average of about 2.76 succinicanhydride functionality per polymer chain.

Example 1J Maleation of Vinyl-Terminated Propylene/1-Hexene Copolymer

To a two-neck 500 ml round-bottomed flask equipped with an N₂ inlet andan N₂ outlet was added vinyl-terminated propylene/1-hexene copolymer(GPC M_(w) 1259, M_(n) 889, ¹H NMR Mn 846.53 g/mol, 150 g, 177.19 mmol)followed by maleic anhydride (43.44 g, 442.99 mmol) at room temperature.The mixture was flushed with nitrogen for 10 min at room temperature andthe mixture was heated to 190° C. (oil bath) for 38.5 hours under anitrogen atmosphere. The mixture was cooled to room temperature, dilutedwith hexanes, filtered and concentrated on a rotary evaporator. Excessmaleic anhydride was removed by heating at 95-100° C. under high vacuumto afford a light brown viscous oily product (178.94 g). GPC M_(w) 1587,M_(n) 1023. Elemental analyses for this propylene/1-hexene succinicanhydride copolymer found C: 80.01%, H: 12.15%. The oxygen content ofthis material is estimated to be about 7.84 wt % by difference. Theanhydride content of this copolymer material is estimated to be about1.633 mmol/g. Based on the molecular weight of polymer startingmaterial, there is an average of about 1.65 succinic anhydridefunctionality per polymer chain.

Example 1K Maleation of Vinyl-Terminated Propylene/1-Hexene Copolymer

To a 300 ml stainless steel autoclave equipped with a mechanical stirrerand an N₂ inlet and an N₂ outlet was added vinyl-terminatedpropylene/1-hexene copolymer (GPC M_(w) 1894, M_(n) 997, ¹H NMR Mn1012.79 g/mol, 90 g, 88.86 mmol) followed by maleic anhydride (20.91 g,213.24 mmol) at room temperature. The mixture was stirred and flushedthree times with nitrogen at room temperature and pressurized to about80 psi with nitrogen. The mixture was heated to 250° C. for 3 hours atabout 140 psi and allowed to cool to room temperature. The pressure wasreleased slowly and the autoclave was opened. The mixture was dilutedwith hexanes, filtered under house vacuum and the filtrate wasconcentrated on a rotary evaporator. Excess maleic anhydride was removedby heating at 95° C. under high vacuum to afford a light brown viscousoily product (103.54 g). GPC M_(w) 1937, M_(n) 1058. Elemental analysesfor this propylene/1-hexene succinic anhydride copolymer found C:80.79%, H: 12.61%. The oxygen content of this material is estimated tobe about 6.60 wt % by difference. The anhydride content of thiscopolymer material is estimated to be about 1.375 mmol/g. Based on themolecular weight of polymer starting material, there is an average ofabout 1.61 succinic anhydride functionality per polymer chain.

Example 1L Maleation of Vinyl-Terminated Propylene/1-Butene Copolymer

To a two-neck 250 ml round-bottomed flask equipped with an N₂ inlet andan N₂ outlet was added vinyl-terminated propylene/1-butene copolymer(GPC M_(w) 2197, M_(n) 1030, ¹H NMR Mn 1062.16 g/mol, 50 g, 47.07 mmol)followed by maleic anhydride (9.23 g, 94.13 mmol) at room temperature.The mixture was flushed with nitrogen for 10 min at room temperature andthe mixture was heated to 190° C. (oil bath) for 84.5 hours under anitrogen atmosphere. The mixture was cooled to room temperature, dilutedwith hexanes, filtered and concentrated on a rotary evaporator. Excessmaleic anhydride was removed by heating at 95-100° C. under high vacuumto afford a light brown viscous oily product (54.97 g). The molecularweight of the product, M_(w) 2294, M_(n) 1242, determined by GPC.Elemental analyses for this propylene/1-butene succinic anhydridecopolymer found C: 81.76%, H: 13.09%. The oxygen content of thismaterial is estimated to be about 5.15 wt % by difference. The anhydridecontent of this copolymer material is estimated to be about 1.073mmol/g. Based on the molecular weight of polymer starting material,there is an average of about 1.27 succinic anhydride functionality perpolymer chain.

Example 1M Condensation of Polypropylene Succinic Anhydride withTetraethylenepentamine (DMA2)

A mixture of polypropylene succinic anhydride (28.00 g, from Example 1G,39.09 mmol anhydride) and xylenes (85 ml) was stirred at roomtemperature under a nitrogen atmosphere and a solution oftetraethylenepentamine (4.11 g, 21.71 mmol) in xylenes (15 ml) wasslowly added. The resulting mixture was heated in an oil bath at 170° C.for 24 hours under a nitrogen atmosphere and an azeotropic mixture ofxylenes and water was collected in a Dean-Stark trap. The light brownmixture was cooled to room temperature and excess xylenes removed on arotary evaporator. The residual liquid product was further purified byheating at 95° C. under high vacuum to afford a dark brown viscousproduct (28.21 g), whose M_(w) was determined to be 4738 by GPC.Elemental analyses for this PP-SA-TEPA material found C: 79.04%, H:12.46%, N: 5.07%.

Example 1N Condensation of Propylene/1-Hexene Succinic Anhydride(C₃C₆-SA) with Tetraethylenepentamine (TEPA)

A mixture of propylene/1-hexene succinic anhydride (30.00 g, fromExample 1J, 48.99 mmol anhydride) and xylenes (85 ml) was stirred atroom temperature under a nitrogen atmosphere and a solution oftetracthylenepentamine (4.22 g, 22.29 mmol) in xylenes (15 ml) wasslowly added. The resulting mixture was heated in an oil bath at 165° C.for 24 hours under a nitrogen atmosphere and an azeotropic mixture ofxylenes and water was collected in a Dean-Stark trap. The light brownmixture was cooled to room temperature and excess xylenes removed on arotary evaporator. The residual liquid product was further purified byheating at 95° C. under high vacuum to afford a brown viscous product(33.24 g), whose molecular weight M_(w) was determined to be 4684 byGPC. Elemental analyses for this C₃C₆-SA-TEPA material found C: 77.96%,H: 12.11%, N: 4.46%.

Example 1P Condensation of Propylene/1-Butene Succinic Anhydride(C₃C₄-SA) with Tetraethylenepentamine (TEPA)

A mixture of propylene/1-butene succinic anhydride (25.00 g, fromExample 1L, 26.83 mmol anhydride) and xylenes (85 ml) was stirred atroom temperature under a nitrogen atmosphere and a solution oftetraethylenepentamine (3.38 g, 17.86 mmol) in xylenes (15 ml) wasslowly added. The resulting mixture was heated in an oil bath at 165° C.for 24 hours under a nitrogen atmosphere and an azeotropic mixture ofxylenes and water was collected in a Dean-Stark trap. The light brownmixture was cooled to room temperature and excess xylenes removed on arotary evaporator. The residual liquid product was further purified byheating at 95° C. under high vacuum to afford a dark brown viscousproduct (27.57 g), whose molecular weight M_(w) was determined to be3878 by GPC. Elemental analyses for this C₃C₄-SA-TEPA material found C:79.71%. H: 13.04%, N: 4.31%.

Example 1Q Copolymerization of Vinyl-Terminated Atactic Polypropylenewith Maleic Anhydride

A mixture of vinyl-terminated atactic polypropylene (NB#25136-002-001,GPC M_(w) 2301, M_(n) 1180, ¹H NMR Mn 944.7 g/mol, 15.00 g, 15.88 mmol),maleic anhydride (2.49 g, 25.39 mmol) and xylenes (14 ml) was heated to150° C. (oil bath temperature) under a nitrogen atmosphere. A solutionof di-tert-butyl peroxide (0.244 g, 1.67 mmol) in xylenes (5 ml) wasadded slowly to the mixture over 1 hour while the oil bath wasmaintained at 150° C. After complete addition of the peroxide solution,the mixture was heated at 155° C. for 4.5 hours and then at 160° C. for1 hour under a nitrogen atmosphere. The mixture was cooled to roomtemperature and excess solvent and volatile material were removed on arotary evaporator. The crude product was further purified by heating at95° C. under high vacuum to afford a light yellow viscous material(17.26 g). The conversion of polypropylene starting material was about81% according to ¹H NMR spectroscopy. The molecular weight of thematerial was determined to be M_(w) 4247, M_(n) 1977 (by GPC). Elementalanalyses for this PP-MA copolymer material found C: 81.01%, H: 12.56%.The oxygen content of this material is estimated to be about 6.43 wt %by difference. The anhydride content of this polymer material isestimated to be about 1.340 mmol/g.

Example 1R Copolymerization of Vinyl-Terminated Atactic Polypropylenewith Maleic Anhydride

A mixture of vinyl-terminated atactic polypropylene (GPC M_(w) 4453,M_(n) 2087, ¹H NMR Mn 1751.5 g/mol, 30.00 g, 17.13 mmol), maleicanhydride (2.69 g, 27.43 mmol) and xylenes (17 ml) was heated to 148° C.(oil bath temperature) under a nitrogen atmosphere. A solution ofdi-tert-butyl peroxide (0.426 g, 2.91 mmol) in xylenes (5 ml) was addedslowly to the mixture over 2 hours while the oil bath was maintained at148° C. After complete addition of the peroxide solution, the mixturewas heated at 148° C. for 4.5 hours under a nitrogen atmosphere.Additional di-tert-butyl peroxide (0.15 g, 1.03 mmol) in xylenes (5 ml)was added to the mixture and heating was continued at 148° C. for anadditional 4.5 hours. A further additional amount of di-tert-butylperoxide (0.15 g, 1.03 mmol) in xylenes (5 ml) was added to the mixtureand heating was continued at 148° C. for an additional 3.5 hours. Themixture was cooled to room temperature and excess solvent and volatilematerial were removed on a rotary evaporator. The crude product wasfurther purified by heating at 95° C. under high vacuum to afford acolorless viscous material (33.10 g). The conversion of polypropylenestarting material was about 83% according to ¹H NMR spectroscopy. Themolecular weight of the material was determined as M_(w) 6552, M_(n)2539 (by GPC). Elemental analyses for this PP-MA copolymer materialfound C: 82.89%, H: 13.10%. The oxygen content of this material isestimated to be about 4.01 wt % by difference. The anhydride content ofthis polymer material is estimated to be about 0.835 mmol/g.

Example 1S Copolymerization of Vinyl-Terminated Propylene/1-HexeneCopolymer with Maleic Anhydride

A mixture of vinyl-terminated propylene/1-hexene copolymer (GPC M_(w)3157, M_(n) 1453, ¹H NMR Mn 1567.2 g/mol, 30.00 g, 19.14 mmol), maleicanhydride (3.75 g, 38.24 mmol) and xylenes (18 ml) was heated to 163° C.(oil bath temperature) under a nitrogen atmosphere. A solution ofdi-tert-butyl peroxide (0.560 g, 3.83 mmol) in xylenes (8 ml) was addedslowly to the mixture over 80 minutes while the oil bath was maintainedat 163° C. After complete addition of the peroxide solution, the mixturewas heated at 163° C. for 15.5 hours under a nitrogen atmosphere. Themixture was cooled to room temperature and excess solvent and volatilematerial were removed on a rotary evaporator. The crude product wasfurther purified by heating at 95° C. under high vacuum to afford alight yellow viscous material (34.22 g). The conversion ofpropylene/1-hexene copolymer starting material was about 87% accordingto ¹H NMR spectroscopy. Elemental analyses for this C₃C₆-MA copolymermaterial found C: 81.79%, H: 13.02%. The oxygen content of this materialis estimated to be about 5.19 wt % by difference. The anhydride contentof this polymer material is estimated to be about 1.081 mmol/g.

Example 1T Functionalization of Polypropylene Maleic Anhydride Copolymerwith Tetraethylenepentamine

A mixture of polypropylene/maleic anhydride (PP-MA) copolymer (6.00 g,from Example 1Q, 8.04 mmol anhydride) and xylenes (45 ml) was stirred atroom temperature under a nitrogen atmosphere and a solution oftetraethylenepentamine (1.17 g, 6.18 mmol) in xylenes (5 ml) was slowlyadded. The resulting mixture was heated in an oil bath at 170° C. for 72hours under a nitrogen atmosphere and an azeotropic mixture of xylenesand water was collected in a Dean-Stark trap. The light brown mixturewas cooled to room temperature and excess xylenes removed on a rotaryevaporator. The residual product was further purified by heating at 95°C. under high vacuum to afford a light brown viscous product (6.92 g).The molecular weight of this product was determined as M_(w) 4247, M_(n)1302 (by GPC). Elemental analyses for this PP-MA-TEPA copolymer additivefound C: 78.00%, H: 12.43%, N: 5.70%.

Example 1U Functionalization of Polypropylene-Maleic Anhydride Copolymerwith Tetraethylenepentamine

A mixture of polypropylene/maleic anhydride (PP-MA) copolymer (8.00 g,from Example 1R, 6.68 mmol anhydride) and xylenes (55 ml) was stirred atroom temperature under a nitrogen atmosphere and a solution oftetraethylenepentamine (0.90 g, 4.75 mmol) in xylenes (5 ml) was slowlyadded. The resulting mixture was heated in an oil bath at 170° C. for 48hours under a nitrogen atmosphere and an azeotropic mixture of xylenesand water was collected in a Dean-Stark trap. The light brown mixturewas cooled to room temperature and excess xylenes removed on a rotaryevaporator. The residual product was further purified by heating at 95°C. under high vacuum to afford a light brown viscous product (8.66 g),whose molecular weight Mw was determined to be 8440 by GPC. Elementalanalyses for this PP-MA-TEPA copolymer additive found C: 80.47%, H:12.92%, N: 3.62%.

Example 1V Functionalization of Propylene/1-Hexene-Maleic AnhydrideCopolymer with Triethylenetetramine

A mixture of vinyl-terminated propylene/1-hexene-maleic anhydride(C₃C₆-MA) copolymer (8.00 g, from Example 1S, 8.65 mmol anhydride) andxylenes (55 ml) was stirred at room temperature under a nitrogenatmosphere and a solution of triethylenetetramine (0.903 g, 6.18 mmol)in xylenes (5 ml) was slowly added. The resulting mixture was heated inan oil bath at 165° C. for 24 hours under a nitrogen atmosphere and anazeotropic mixture of xylenes and water was collected in a Dean-Starktrap. The light brown mixture was cooled to room temperature and excessxylenes removed on a rotary evaporator. The residual product was furtherpurified by heating at 95° C. under high vacuum to afford a light brownviscous product (8.70 g), whose molecular weight Mw was determined to be5690 by GPC. Elemental analyses for this C₃C₆-MA-TEPA copolymer additivefound C: 80.39%, H: 12.78%, N: 3.62%.

Example 2 Fouling Reduction Measured in the Alcor HLPS (Hot LiquidProcess Simulator)

FIG. 2 depicts an Alcor HLPS (Hot Liquid Process Simulator) testingapparatus used to measure the impact of addition of particulates to acrude oil on fouling and the impact the addition of an additive of thedisclosed subject matter has on the mitigation of fouling. The testingarrangement includes a reservoir 10 containing a feed supply of crudeoil. The feed supply of crude oil can contain a base crude oilcontaining a whole crude or a blended crude containing two or more crudeoils. The feed supply is heated to a temperature of approximately 150°C./302° F. and then fed into a shell 11 containing a vertically orientedheated rod 12. The heated rod 12 is formed from carbon-steel (1018). Theheated rod 12 simulates a tube in a heat exchanger. The heated rod 12 iselectrically heated to a surface temperature of 370° C./698° F. or 400°C./752° F. and maintained at such temperature during the trial. The feedsupply is pumped across the heated rod 12 at a flow rate ofapproximately 3.0 mL/minute. The spent feed supply is collected in thetop section of the reservoir 10. The spent feed supply is separated fromthe untreated feed supply oil by a sealed piston, thereby allowing foronce-through operation. The system is pressurized with nitrogen (400-500psig) to ensure gases remain dissolved in the oil during the test.Thermocouple readings are recorded for the bulk fluid inlet and outlettemperatures and for surface of the rod 12.

During the constant surface temperature testing, foulant deposits andbuilds up on the heated surface. The foulant deposits are thermallydegraded to coke. The coke deposits cause an insulating effect thatreduces the efficiency and/or ability of the surface to heat the oilpassing over it. The resulting reduction in outlet bulk fluidtemperature continues over time as fouling continues. This reduction intemperature is referred to as the outlet liquid ΔT or ΔT and can bedependent on the type of crude oil/blend, testing conditions and/orother effects, such as the presence of salts, sediment or other foulingpromoting materials. A standard Alcor fouling test is carried out for180 minutes. The total fouling, as measured by the total reduction inoutlet liquid temperature over time, is plotted on the y-axis of FIGS.5-11 and is the observed outlet temperature (T_(outlet)) minus themaximum observed outlet T_(outlet max) (presumably achieved in theabsence of any fouling).

Example 2A

Antifouling Additive 1 (“AFA1”), a commercially available preparation ofpolyisobutylene-succinic anhydride-polyamine (PIB-SA-PAM) was added tocrude oil to a concentration of 374 ppm. 11 cc of water was then addedto said mixture and blended for 10 seconds at 50% power using a Waringblender to generate a water-in-oil emulsion. 200 cc of said emulsion wasplaced into two separate Electrostatic Dehydration and PrecipitationTester (EDPT) transparent vessels (available from Inter AV Inc.) and avoltage of 3500 volts was applied to the emulsion at an interval of 2minutes for a duration of 16 minutes at room temperature. 120 ml of thedehydrated crude was then added to 680 ml of the original crude oil withpre-added iron oxide and mixed well. The final concentration of ironoxide in the resulting crude oil blend is 200 wppm, and the finalconcentration of AFA1 is approximately 50 wppm. This crude blendcontaining AFA1 and iron oxide was subsequently evaluated forantifouling as described below and as illustrated in FIG. 3.

FIG. 3 illustrates the impact of fouling of a refinery component over180 minutes. Two blends were tested in the Alcor unit: a crude oilcontrol containing added rust (iron oxide) particles (200 wppm) withoutan additive, and the crude oil blend prepared as noted above containing200 wppm of iron oxide and approximately 50 wppm AFA1. As FIG. 3demonstrates, the reduction in the outlet temperature over time (due tofouling) is less for the process blend containing the additive AFA1 ascompared to the crude oil control without the additive. This indicatesthat the additive remains in the crude during the dehydration andelectrocoalescence processes and is able to effectively reduce foulingof a heat exchanger.

Example 2B

Antifouling Additive 2 (“AFA2”), polypropylene-succinicanhydride-polyamine (PP-SA-PAM) prepared according to Example 1E above,was added to crude oil to a concentration of 374 ppm. 11 cc of water wasthen added to said mixture and blended for 10 seconds at 50% power usinga Waring blender to generate a water-in-oil emulsion. 200 cc of saidemulsion was placed into two separate Electrostatic Dehydration andPrecipitation Tester (EDPT) transparent vessels and a voltage of 3500volts was applied to the emulsion at an interval of 2 minutes for aduration of 16 minutes at room temperature. 120 ml of the dehydratedcrude was then added to 680 ml of the original crude oil with pre-addediron oxide and mixed well. The final concentration of iron oxide in theresulting crude oil blend is 200 wppm, and the final concentration ofAFA2 is approximately 50 wppm. It was assumed that the antifoulingadditive localized to the crude phase and was not degraded duringdehydration. This crude blend containing AFA2 and iron oxide wassubsequently evaluated for antifouling as described below and asillustrated in FIG. 4.

FIG. 4 illustrates the impact of fouling of a refinery component over180 minutes. Two blends were tested in the Alcor unit: a crude oilcontrol containing 200 wppm of added rust (iron oxide) particles withoutan additive, and the crude oil blend prepared above containing 200 wppmof iron oxide and approximately 50 wppm AFA2. As FIG. 4 demonstrates,the reduction in the outlet temperature over time (due to fouling) isless for the process blend containing the additive AFA2 as compared tothe crude oil control without the additive. This indicates that theadditive is effective at reducing fouling of a heat exchanger.

Example 2C

FIG. 5 illustrates the impact of fouling of a refinery component over180 minutes. Two blends were tested in the Alcor unit: a crude oilcontrol containing added rust (iron oxide) particles (200 wppm) withoutan additive, and the same stream with 25 wppm of the additive preparedin Example 1M. As FIG. 5 demonstrates, the reduction in the outlettemperature over time (due to fouling) is less for the process blendcontaining the additive as compared to the crude oil control without theadditive. This indicates that the additive is effective at reducingfouling of a heat exchanger.

Example 2D

FIG. 6 illustrates the impact of fouling of a refinery component over180 minutes. Two blends were tested in the Alcor unit: a crude oilcontrol containing added rust (iron oxide) particles (200 wppm) withoutan additive, and the same stream with 50 wppm of the additive preparedin Example 1T. As FIG. 6 demonstrates, the reduction in the outlettemperature over time (due to fouling) is less for the process blendcontaining the additive as compared to the crude oil control without theadditive. This indicates that the additive is effective at reducingfouling of a heat exchanger.

Example 2E

FIG. 7 illustrates the impact of fouling of a refinery component over180 minutes. Two blends were tested in the Alcor unit: a crude oilcontrol containing added rust (iron oxide) particles (200 wppm) withoutan additive, and the same stream with 50 wppm of the additive preparedin Example 1U. As FIG. 7 demonstrates, the reduction in the outlettemperature over time (due to fouling) is less for the process blendcontaining the additive as compared to the crude oil control without theadditive. This indicates that the additive is effective at reducingfouling of a heat exchanger.

Example 2F

FIG. 8 illustrates the impact of fouling of a refinery component over180 minutes. Two blends were tested in the Alcor unit: a crude oilcontrol containing added rust (iron oxide) particles (200 wppm) withoutan additive, and the same stream with 25 wppm of the additive preparedin Example 1V. As FIG. 8 demonstrates, the reduction in the outlettemperature over time (due to fouling) is less for the process blendcontaining the additive as compared to the crude oil control without theadditive. This indicates that the additive is effective at reducingfouling of a heat exchanger.

Example 2G

FIG. 9 illustrates the impact of fouling of a refinery component over180 minutes. Two blends were tested in the Alcor unit: a crude oilcontrol containing added rust (iron oxide) particles (200 wppm) withoutan additive, and the same stream with 25 ppm and 50 wppm of the additiveprepared in Example 1U. As FIG. 9 demonstrates, the reduction in theoutlet temperature over time (due to fouling) is less for the processblend containing the additive as compared to the crude oil controlwithout the additive. This indicates that the additive is effective atreducing fouling of a heat exchanger.

ADDITIONAL EMBODIMENTS

Additionally or alternately, the invention can include one or more ofthe following embodiments.

Embodiment 1

A compound for treating an emulsion of crude hydrocarbon and/or reducingfouling of a crude hydrocarbon in a hydrocarbon refining process, thecompound represented by:

wherein: m and n are each independently selected from an integer between0 and 10 inclusive; R₁ is a branched or straight-chained C₁₀-C₈₀₀ alkylor alkenyl group; R₂ is a C₁-C₄ branched or straight chained alkylenegroup; R₃ is a C₁-C₄ branched or straight chained alkylene group; R₃₁ ishydrogen or —R₈-R₉, wherein R₈ is C₁-C₄ branched or straight chainedalkylene group, and R₉ is

wherein R₉₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup; or R₈ and R₉ together are a C₁-C₄ branched or straight chainedalkyl group optionally substituted with one or more amine groups: andfurther wherein the —N(R₃₁)-R₃— repeat unit is optionally interrupted inone or more places by a nitrogen-containing heterocyclic cycloalkylgroup; and R₄ and R₅ are each independently selected from (a) hydrogen:(b) a bond connected to R₃₁ in the last distal —N(R₃₁)-R₃— repeat unit:or (c) —R₆-R₇, wherein R₆ is C₁-C₄ branched or straight chained alkylenegroup, and R₇ is

wherein R₇₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup; and wherein the groups R₂′, R₃′, R₃₁′, R₄′ and R₅′ are eachdefined the same as R₂, R₃, R₃₁ and R₄, and R₅, respectively.

Embodiment 2

A compound for treating an emulsion of crude hydrocarbon and/or reducingfouling of a crude hydrocarbon in a hydrocarbon refining process, thecompound represented by:

wherein: m is an integer between 0 and 10 inclusive;

z is 1 or 2, and y is an integer between 1 and 5 inclusive;

R₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenyl group; R₂is a C₁-C₄ branched or straight chained alkylene group; R₃ is a C₁-C₄branched or straight chained alkylene group; R₃₁ is hydrogen or —R₈-R₉,wherein R₈ is C₁-C₄ branched or straight chained alkylene group, and R₉is

wherein R₉₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup; or R₈ and R₉ together are a C₁-C₄ branched or straight chainedalkyl group optionally substituted with one or more amine groups; andfurther wherein the —N(R₃₁)-R₃— repeat unit is optionally interrupted inone or more places by a nitrogen-containing heterocyclic cycloalkylgroup; and R₄ and R₅ are each independently selected from (a) hydrogen;(b) a bond connected to R₃₁ in the m-th —N(R₃₁)-R₃— repeat unit; or (c)—R₆-R₇, wherein R₆ is C₁-C₄ branched or straight chained alkylene group,and R₇ is

wherein R₇₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup.

Embodiment 3

The compound according to any one of Embodiment 1 or Embodiment 2,wherein at least one of R₁, R₇₁, and R₉₁ comprises polypropylene.

Embodiment 4

The compound according to Embodiment 3, wherein the polypropylene isselected from the group consisting of atactic polypropylene, isotacticpolypropylene, syndiotactic polypropylene, amorphous polypropylene,polypropylene including isotactic crystallizable units, polypropyleneincluding syndiotactic crystallizable units, and polypropylene includingmeso diads constituting from about 30% to about 99.5% of the total diadsof the polypropylene.

Embodiment 5

The compound of Embodiment 3, wherein at least one of R₁, R₇₁, and R₉₁has a number-averaged molecular weight of from about 300 to about 30000g/mol.

Embodiment 6

The compound of any one of Embodiment 1 or Embodiment 2, wherein atleast one of R₁, R₇₁, and R₉₁ comprises polyethylene.

Embodiment 7

The compound of claim any one of Embodiment 1 or Embodiment 2, whereinat least one of R₁, R₇₁, and R₉₁ comprises poly(ethylene-co-propylene).

Embodiment 8

The compound of Embodiment 7, wherein at least one of R₁, R₇₁, and R₉₁comprises from about 1 mole % to about 90 mole % of ethylene units andfrom about 99 mole % to about 10 mole % propylene units.

Embodiment 9

The compound of Embodiment 8, wherein at least one of R₁, R₇₁, and R₉₁comprises from about 10 mole % to about 50 mole % of ethylene units.

Embodiment 10

The compound of any one of Embodiment 1 or Embodiment 2, wherein atleast one of R₁, R₇₁, and R₉₁ comprises poly(higher alpha-olefin), thehigher alpha-olefin including two or more carbon atoms on each sidechain.

Embodiment 11

The compound of any one of Embodiment 1 or Embodiment 2, wherein atleast one of R₁, R₇₁, and R₉₁ comprises poly(propylene-co-higheralpha-olefin), the higher alpha-olefin including two or more carbonatoms on each side chain.

Embodiment 12

The compound of any one of Embodiment 1 or Embodiment 2, wherein thenitrogen content in the compound is about 1 wt % to about 10 wt % of thetotal weight of the compound.

Embodiment 13

The compound of any one of Embodiment 1 or Embodiment 2, wherein R; is—CH₂—CH₂—, and R₃₁ is hydrogen.

Embodiment 14

The compound of Embodiment 13, wherein the —N(R₃₁)—R₃— repeat unit isinterrupted in one or more places by a 1,4-diethylenediamine.

Embodiment 15

A method for reducing fouling in a hydrocarbon refining processcomprising providing a crude hydrocarbon for a refining process; andadding an additive to the crude hydrocarbon, wherein the additive isselected from one of the compounds set forth in any one of Embodiments1-14.

Embodiment 16

A method for preparing a compound for treating an emulsion of crudehydrocarbon and/or reducing fouling of a crude hydrocarbon in ahydrocarbon refining process, comprising:

(a) reacting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, with maleic anhydride to obtain a polymer represented by FormulaI below:

wherein R₂₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup;

(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)-R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)-R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

Embodiment 17

A method for preparing a compound for treating an emulsion of crudehydrocarbon and/or reducing fouling of a crude hydrocarbon in ahydrocarbon refining process, the method comprising:

(a) reacting a polymer base unit R₁₁, which is a branched orstraight-chained C₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminalgroup, with maleic anhydride to obtain a polymer represented by FormulaII below:

wherein R₂₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup, z is 1 or 2, and y is an integer between 1 and 5 inclusive:

(b) reacting the polymer obtained in (a) with a polyamine represented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups. R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)-R₁₃-unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)-R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.

Embodiment 18

The method according to any one of Embodiment 16 and Embodiment 17,wherein the molar ratio of R₁₁:polyamine is between about 5:1 and about1:1.

Embodiment 19

The method according to any one of Embodiment 16 and Embodiment 17,wherein at least 50% of the terminal vinyl groups of R₁₁ are an allylicvinyl group.

Embodiment 20

The method according to any one of Embodiment 16 and Embodiment 17,wherein the polyamine comprises linear, branched or cyclic isomers of anoligomer of ethyleneamine, or mixtures thereof, wherein each twoneighboring nitrogens in the oligomer of ethyleneamine are bridged byone or two ethyleneamine groups.

Embodiment 21

The method according to Embodiment 20, wherein the polyamine is selectedfrom ethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine,and mixtures thereof.

Embodiment 22

The method according to any one of Embodiment 16 and Embodiment 17,wherein the polyamine comprises a heavy polyamine.

Embodiment 23

The method according to any one of Embodiment 16 and Embodiment 17,wherein (a) comprises reacting the polymer base unit R₁₁ with maleicanhydride at a ratio R₁₁:maleic anhydride of between about 1:1 to about1:5.

Embodiment 24

The method according to any one of Embodiment 16 and Embodiment 17,wherein (a) comprises reacting the polymer base unit R₁₁ with maleicanhydride without an additional initiator providing a radical species.

Embodiment 25

A compound for reducing fouling of a crude hydrocarbon in a hydrocarbonrefining process, the compound prepared by the method according to anyone of Embodiments 16 and 18-24.

Embodiment 26

A compound for treating an emulsion of crude hydrocarbon and/or reducingfouling of a crude hydrocarbon in a hydrocarbon refining process, thecompound prepared by the method according to any one of Embodiments17-24.

The disclosed subject matter is not to be limited in scope by thespecific embodiments described herein. Indeed, various modifications ofthe invention in addition to those described herein will become apparentto those skilled in the art from the foregoing description and theaccompanying figures. Such modifications are intended to fall within thescope of the appended claims.

It is further to be understood that all values are approximate, and areprovided for description.

Patents, patent applications, publications, product descriptions, andprotocols are cited throughout this application, the disclosures of eachof which is incorporated herein by reference in its entirety for allpurposes.

1.-13. (canceled)
 14. A method for preparing a compound for treating anemulsion of crude hydrocarbon and/or reducing fouling of a crudehydrocarbon in a hydrocarbon refining process, comprising: (a) reactinga polymer base unit R₁₁, which is a branched or straight-chainedC₁₀-C₈₀₀ alkyl or alkenyl group having a vinyl terminal group, withmaleic anhydride to obtain a polymer represented by Formula I below:

wherein R₂₁ is a branched or straight-chained C₁₀-C₈₀₀ alkyl or alkenylgroup; (b) reacting the polymer obtained in (a) with a polyaminerepresented by

wherein R₁₂ is hydrogen or a C₁-C₄ branched or straight chained alkyloptionally substituted with one or more amine groups, R₁₃ is a C₁-C₄branched or straight chained alkylene group, and x is an integer between1 and 10, and further wherein the —N(R₁₂)-R₁₃— unit is optionallyinterrupted in one or more places by a nitrogen-containing heterocycliccycloalkyl group, and wherein when the x-th —N(R₁₂)-R₁₃— unit along withthe terminal nitrogen atom forms a heterocyclic cycloalkyl group, theterminal —NH₂ is replaced by a —NH— group for valency.
 15. The method ofclaim 14, wherein the molar ratio of R₁₁:polyamine is between about 5:1and about 1:1.
 16. The method of claim 14, wherein at least 50% of theterminal vinyl groups of R₁₁ are an allylic vinyl group.
 17. The methodof claim 14, wherein the polyamine comprises linear, branched or cyclicisomers of an oligomer of ethyleneamine, or mixtures thereof, whereineach two neighboring nitrogens in the oligomer of ethyleneamine arebridged by one or two ethyleneamine groups.
 18. The method of claim 17,wherein the polyamine is selected from ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, hexaethyleneheptamine, and mixtures thereof. 19.The method of claim 14, wherein the polyamine comprises a heavypolyamine.
 20. The method of claim 14, wherein (a) comprises reactingthe polymer base unit R₁₁ with maleic anhydride at a ratio R₁₁:maleicanhydride of between about 1:1 to about 1:5.
 21. The method of claim 14,wherein (a) comprises reacting the polymer base unit R₁₁ with maleicanhydride without an additional initiator providing a radical species.22.-57. (canceled)